Process for producing α-olefin polymers

ABSTRACT

A process for producing α-olefin polymers is provided which comprises: 
     reacting an organoaluminum compound (A 1 ) with an electron donor (B 1 ) to obtain a reaction product (I); 
     reacting (I) with TiCl 4  to obtain a solid product (II); 
     reacting (II) with an electron donor (B 2 ) and an electron acceptor to obtain a solid product (III); 
     combining (III) with an organoaluminum compound (A 2 ) and a reaction product (G) of an organoaluminum (A 3 ) with an electron donor (B 3 ) ((III), (A 2 ) and (G) being referred to as catalyst components), and in this combination, subjecting a part or the whole of the catalyst components to polymerization treatment with an α-olefin at least in the presence of (III) and said (A 2 ) to obtain a preliminarily activated catalyst; 
     and 
     polymerizing an α-olefin in the presence of the catalyst. According to this process, even in the case of gas phase polymerization, the resulting polymer has a uniform particle size; the catalyst employed has not only a high stability but also a high activity whereby the advantages of gas phase polymerization can be fully exhibited; and further it is possible to easily control the stereoregularity of polymer.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a process for producing α-olefin polymers bythe use of a novel catalyst which is suitable for α-olefinpolymerization, particularly gas phase polymerization, and further, as amodification of gas phase polymerization, a combination of slurry orbulk polymerization with gas phase polymerization.

2. Description of the Prior Art

It is well known that α-olefins are polymerized by the use of so-calledZiegler-Natta catalysts comprising a compound of transition metals ofIV-VI Groups of the Periodic Table and an organometallic compound ofmetals of I-III Groups of the Table, including modified catalystsobtained by further adding an electron donor, etc. thereto. Among thecatalysts, those comprising titanium trichloride as the component oftransition metal compound have been most widely employed for obtaininghighly crystalline polymers of e.g. propylene, butene-1, etc. Suchtitanium trichloride is classified into the following three kindsaccording to its preparation:

(1) A material obtained by reducing TiCl₄ with hydrogen, followed bymilling with ball mill for activation, which material has been referredto as titanium trichloride (HA).

(2) A material obtained by reducing TiCl₄ with metallic aluminum,followed by milling with ball mill for activation, which material isexpressed by the general formula TiCl₃ ·1/3AlCl₃ and has been referredto as titanium trichloride (AA).

(3) A material obtained by reducing TiCl₄ with an organoaluminumcompound, followed by heat treatment.

However, since any of these titanium trichlorides have not beensatisfactory enough, various improvements have been attempted andproposed. Among them, a process has been proposed wherein a titaniumtrichloride obtained by reducing TiCl₄ with an organoaluminum compoundis treated with an electron donor and TiCl₄ whereby the catalystactivity is enhanced and the amount of amorphous polymer byproduced isreduced (e.g. Japanese patent application laid-open No. 34478/1972).However, the catalysts obtained according to these processes have adrawback that they are deficient in the heat stability.

Further, a process has been proposed wherein TiCl₄ and an organoaluminumcompound are separately mixed with a definite amount of acomplex-forming agent (electron donors being a kind thereof), to obtaintwo mixture liquids which are then mixed together and reacted to preparea solid catalyst component (Japanese patent application laid-open No.9296/1978). However, this process, too, has a drawback that the catalystis deficient in the heat stability, as in the case of the above Japanesepatent application laid-open No. 34478/1972.

Still further, a process wherein a uniform liquid material consisting ofan organoaluminum compound and an ether is added to TiCl₄ or TiCl₄ isadded to the former liquid to prepare a liquid material containingtitanium trichloride (Japanese patent application laid-open No.115797/1977), as well as a process wherein the above-mentioned liquidmaterial is heated to a temperature of 150° C. or lower to precipitate afinely particulate titanium trichloride (Japanese patent applicationlaid-open No. 47594/1977, etc.) have been proposed.

However, these processes, too, have a drawback that the catalysts aredeficient in the heat stability.

On the other hand, as for processes for polymerizing α-olefins whereinZeigler-Natta catalysts are employed but the phase of α-olefins isvaried, slurry polymerization carried out in a solvent such as n-hexane,etc. (e.g. Japanese patent publication No. 10596/1957), bulkpolymerization carried out in a liquefied α-olefin monomer such asliquefied propylene (e.g. Japanese patent publication Nos. 6686/1961,14041/1963), and gas phase polymerization carried out in a gaseousmonomer such as gaseous propylene (e.g. Japanese patent publication Nos.14812/1964, 17487/1967, etc.), have been well known. Further, a processof bulk polymerization followed by gas phase polymerization has beenalso known (e.g. Japanese patent publication No. 14862/1974, Japanesepatent application laid-open No. 135987/1976, etc.). Among thesepolymerization processes, gas phase one is advantageous in that recoveryand reuse of solvent employed in polymerization as in the case of slurrypolymerization process are unnecessary; recovery and reuse of liquefiedmonomer such as liquefied propylene as in the case of bulkpolymerization process are unnecessary; hence the cost of solvent ormonomer recovery is small to simplify the equipments for producingα-olefin polymers; etc. These gas phase polymerization processes,however, have had such disadvantages that since the monomer inside thepolymerization vessel is present in vapor phase, the monomerconcentration is relatively low as compared with those in slurry or bulkpolymerization process, resulting in a lower reaction rate; thus, inorder to increase the polymer yield per unit weight of catalyst, it hasbeen necessary to extend the retention time and hence make the capacityof the reactor larger, and also, in order to enhance the catalystactivity, trialkylaluminums have been modified and used, resulting inreduction of the stereoregularity of polymer. In the case of gas phasepolymerization process, however, uneven catalyst particles are liable toresult in uneven polymer particles. This is, in turn, liable to causecohesion of polymer particles and clogging of polymer-discharging portof polymerization vessel or transportation line, to make difficult itslong time, stabilized, continuous operation and also make the qualitydispersion of polymers larger.

The present inventors have previously invented a polymerization processfree of the above-mentioned drawbacks even in the case of gas phasepolymerization, that is, a process for producing α-olefin polymers usinga catalyst prepared by reacting a reaction product of an electron donorwith an organoaluminum compound, with TiCl₄, in the presence of anaromatic compound to form a solid product, or reacting this solidproduct further with an electron donor to form a solid product; andcombining the solid product thus obtained, with an organoaluminumcompound.

The inventors have further made studies, and as a result, have inventeda process comprising reacting an organoaluminum compound with anelectron donor to obtain a reaction product; reacting this reactionproduct with TiCl₄ to obtain a solid product; reacting this solidproduct with an electron donor and an electron acceptor to obtainanother solid product; combining this solid product with anorganoaluminum compound to obtain a catalyst; and polymerizing anα-olefin in the presence of this catalyst (this process will behereinafter referred to as prior invention). According to thispolymerization process, particularly in the case of gas phasepolymerization in the presence of a catalyst obtained by subjecting thecatalyst of the above-mentioned process to a preliminary activation withan α-olefin, a long time stabilized operation without forming anypolymer lump has become possible even in the case of gas phasepolymerization, but the polymer yield per g of the solid catalystcomponent was 5,000 to 6,000 g, i.e. the activity of the catalyst couldnot have been regarded as sufficient. Thus, the amount of catalystemployed could not have been reduced. If the amounts of alcohol,alkylene oxide, steam, etc. employed for killing of catalyst afterproduction of α-olefin polymers or for purification of polymer arereduced too much, then corrosive substances remaining in polymer haveoften been not made unharmless, resulting in rusting of mold at the timeof molding of polymer or harming the physical properties of polymer.

The present inventors further continued studies for improvement, and asa result have found that if an unknown catalyst component is combinedwith the catalyst employed in the prior invention, and in thiscombination, the resulting catalyst components are subjected topolymerization treatment with an α-olefin and employed forpolymerization, then, even in the case of gas phase polymerization, nopolymer lump is not only formed, but also the polymer yield can besufficiently increased and polymer purification can be easily be carriedout; it is possible to produce polymer, particularly polypropylene,under control of its stereoregularity; and the rate of atactic polymerformed is low, and have attained the present invention.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a process forproducing α-olefin polymers wherein, even in the case of gas phasepolymerization, the resulting polymer has a uniform particle size; thecatalyst employed has not only a high stability but also a high activitywhereby the advantages of gas phase polymerization can be fullyexhibited; and further it is possible to easily control thestereoregularity of polymer.

The present invention resides briefly in:

a process for producing α-olefin polymers which comprises:

reacting an organoaluminum compound (A₁) with an electron donor (B₁) toobtain a reaction product (I);

reacting this reaction product (I) with TiCl₄ to obtain a solid product(II);

reacting this solid product (II) with an electron donor (B₂) and anelectron acceptor (E) to obtain a solid product (III);

combining this solid product (III) with an organoaluminum compound (A₂)and a reaction product (G) of an organoaluminum (A₃) with an electrondonor (B₃) (these three substances to be combined together will behereinafter referred to as catalyst components), and in thiscombination, subjecting a part or the whole of the catalyst componentsto polymerization treatment with an α-olefin at least in the presence ofsaid reaction product (III) and said aluminum compound (A₂) to obtain apreliminarily activated catalyst; and

polymerizing an α-olefin or α-olefins in the presence of thispreliminarily activated catalyst.

The terms "polymerization treatment" referred to above means that asmall amount of α-olefin is brought into contact with catalystcomponents under polymerizable conditions and said α-olefin ispolymerized. By this polymerization treatment, the catalyst componentsare brought to a state coated with polymer.

DETAILED DESCRIPTION OF THE INVENTION

The process for preparing the catalyst employed in the present inventionwill be described below.

The preparation of the solid product (III) is carried out as follows:

An organoaluminum compound is first reacted with an electron donor toobtain a reaction product (I), which is then reacted with TiCl₄ toobtain a solid product (II), which is then further reacted with anelectron donor and an electron acceptor to obtain a solid product (III).

The reaction of an organoaluminum compound (A) with an electron donor(B₁) is carried out in a solvent (D), at a temperature of -20° to 200°C., preferably -10° to 100° C. and for a time of 30 seconds to 5 hours.The addition order of (A), (B₁) and (D) has no limitation, and theproportion of the amounts thereof employed is suitably 0.1 to 8 mols,preferably 1 to 4 mols, of an electron donor and 0.5 to 5 l, preferably0.5 to 2 l, of a solvent, per mol of an organoaluminum. Aliphatichydrocarbons are preferable as the solvent. Thus a reaction product (I)is obtained. The reaction product (I) may be subjected to the subsequentreaction, in a state of liquid after completion of the reaction (whichliquid will be hereinafter referred to as reaction liquid (I)), as itis, without separating the solid product (I).

The reaction of the reaction product (I) with TiCl₄ (C) is carried outat a temperature of 0° to 200° C., preferably 10° to 90° C., for 5minutes to 8 hours. Although it is preferable to employ no solvent,aliphatic or aromatic hydrocarbons may be employed as solvent. Additionof (I), (C) and solvent may be carried out in any order, and mixing ofthe total amount is preferably completed within 5 hours. As for theamounts of them employed for the reaction, the amount of solvent is 0°to 3,000 ml per mol of TiCl₄, and the ratio (Al/Ti) of the number of Alatoms in (I) to that of Ti atoms in TiCl₄ is 0.05 to 10, preferably 0.06to 0.2. After completion of the reaction, a liquid portion is separatedand removed by filtration or decantation, followed by repeated washingswith solvent to obtain a solid product (II), which may be employed inthe next step in a state where it is suspended in solvent, as it is, ormay be further dried to employ the resulting solid product in the nextstep.

The solid product (II) is then reacted with an electron donor (B₂) andan electron acceptor (E). Although this reaction may be carried outwithout employing any solvent, employment of aliphatic hydrocarbonsyields preferable results. As for the amounts of them employed, 10 to1,000 g, preferably 50 to 200 g of (B₂), 10 to 1,000 g, preferably 20 to500 g of (E) and 0 to 3,000 ml, preferably 100 to 1,000 ml of solvent,each based on 100 g of the solid product (II) are employed. It ispreferable to admix these 3 or 4 substances at a temperature of -10° to40° C. for a time of 30 seconds to 60 minutes and react them at atemperature of 40° to 200° C., preferably 50° to 100° C. for a time of30 seconds to 5 hours. The order of addition of the solid product (II),(B₂), (E) and solvent has no particular limitation, (B₂) and (E) may bereacted together in advance of mixing them with the solid product (II).The reaction of (B₂) with (E) is carried out at a temperature of 10° to100° C. for a time of 30 minutes to 2 hours, and the resulting productis cooled down to 40° C. or lower and employed. After completion of thereaction of the reaction product (II), (B₂) and (E), a liquid portion isseparated and removed by filtration or decantation, followed by repeatedwashings to obtain a solid product (III), which is employed in the nextstep after dried and taken out as solid matter, or in a state where itis suspended in a solvent, as it is.

The solid product (III) thus obtained is combined with an organoaluminumcompound (A₂), a reaction product (G) of an organoaluminum compound (A₃)with an electron donor (B₃) and an α-olefin (F) to effect a preliminaryactivation of catalyst, and at the same time, the reaction product (G)is adequately selected to obtain a polymer having its stereoregularitycontrolled.

The organoaluminum compounds employed in the present invention areexpressed by the general formula AlR_(n) R'_(n) X₃₋(n+n') wherein R andR' each represent a hydrocarbon group such as alkyl group, aryl group,alkaryl group, cycloalkyl group, etc. or alkoxy group; X represents ahalogen such as fluorine, chlorine, bromine or iodine; and n and n' eachrepresent an optional number of 0<n+n'≦3, and as concrete examples,trialkylaluminums such as trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum,tri-n-hexylaluminum, tri-i-hexylaluminum, tri-2-methylpentylaluminum,tri-n-octylaluminum, tri-n-decylaluminum, etc., dialkylaluminummonohalides such as diethylaluminum monochloride, di-n-propylaluminummonochloride, di-i-butylaluminum monochloride, diethylaluminummonofluoride, diethylaluminum monobromide, diethylaluminum monoiodide,etc.; alkylaluminum hydrides such as diethylaluminum hydride; andalkylaluminum halides such as methylaluminum sesquichloride,ethylaluminum sesquichloride, ethylaluminum dichloride, i-butylaluminumdichloride, etc. are mentioned. Besides, alkoxyalkylaluminums such asmonoethoxydiethylaluminum, diethoxymonoethylaluminum, etc. may be alsoemployed. These organoaluminums may be employed in admixture of two ormore kinds. The organoaluminum compounds (A₁), (A₂) and (A₃) may be thesame or different.

As for the electron donors employed in the present invention, variouskinds are illustrated below, but it is preferable for (B₁) and (B₂) thatelectron donors composed singly or mainly (more than 50% by mol based onthe total mols thereof) of ethers be employed and those other thanethers be employed together with ethers. As for the electron donorsemployed, organic compounds containing at least one atom of oxygen,nitrogen, sulfur and phosphorus, such as ethers, alcohols, esters,aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines,amides, urea, thiourea, isocyanates, azo compounds, phosphines,phosphites, phosphinites, thioethers, thioalcohols, etc. are mentioned.As for concrete examples, ethers such as diethyl ether, di-n-propylether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexylether, di-i-hexyl ether, di-n-octyl ether, di-i-octyl ether,di-n-dodecyl ether, diphenyl ether, ethylene glycol monomethyl ether,diethylene glycol dimethyl ether, tetrahydrofuran; alcohols such asmethanol, ethanol, propanol, butanol, pentanol, hexanol, octanol,phenol, cresol, xylenol, ethylphenol, naphthol; esters such as methylmethacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl lactate,vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octylbenzoate, 2-ethylhexyl benzoate, methyl toluylate, ethyl toluylate,2-ethylhexyl toluylate, methyl anisate, ethyl anisate, propyl anisate,ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate,butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate;aldehydes such as acetaldehyde, benzaldehyde; fatty acids such as formicacid, acetic acid, propionic acid, lactic acid, oxalic acid, succinicacid, acrylic acid, maleic acid; aromatic acids such as benzoic acid;ketones such as methyl ethyl ketone, methyl isobutyl ketone,benzophenone; nitriles such as acetonitrile; amines such as methylamine,diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, pyridine, quinoline, α-picoline,N,N,N',N'-tetramethylhexaethylenediamine, aniline, dimethylaniline;amides such as formamide, hexamethyl phosphoric acid triamide,N,N,N',N',N"-pentamethyl-N'-β-dimethylaminoethyl phosphoric acidtriamide, octamethylpyrophosphoroamide; ureas such asN,N,N',N'-tetramethylurea; isocyanates such as phenylisocyanate,toluylisocyanate; azo compounds such as azobenzene; phosphines such asethylphosphine, triethylphosphine, tri-n-butylphosphine,tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide;phosphites such as dimethylphosphite, di-n-octylphosphite,triethylphosphite, tri-n-butylphosphite, triphenylphosphite;phosphinites such as ethyldiethylphosphinite, ethyldibutylphosphinite,phenyldiphenylphosphinite; thioethers such as diethyl thioether,diphenyl thioether, methyl phenyl thioether, ethylene sulfide, propylenesulfide; and thioalcohols such as ethyl alcohol, n-propyl thioalcohol,thiophenol, are mentioned. These electron donors may be employed inadmixture. The electron donor (B₁) for obtaining the reaction product(I), (B₂) to be reacted with the solid product (II) and (B_(3L) ) forobtaining the solid product (G) may be the same or different,respectively.

The electron acceptors employed in the present invention are representedby halides of elements of III Group to VI Group of the Periodic Table.As concrete examples, anhydrous AlCl₃, SiCl₄, SnCl₂, SnCl₄, TiCl₄,ZrCl₄, PCl₃, PCl₅, VCl₄, SbCl₅, etc. are mentioned. They may be employedin admixture. TiCl₄ is most preferable.

As for the solvent, the following ones are employed: As aliphatichydrocarbons, n-heptane, n-octane, i-octane, etc. are mentioned.Further, in place of the aliphatic hydrocarbons or together therewith,halogenated hydrocarbons such as carbon tetrachloride, chloroform,dichloroethylene, trichloroethylene, tetrachloroethylene, etc. may bealso employed. As for aromatic compounds, aromatic hydrocarbons such asnaphthalene, and as their derivatives, alkyl substitutes such asmesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene,1-phenylnaphthalene, etc., and halides such as monochlorobenzene,o-dichlorobenzene, etc. are mentioned.

Next, the process of preliminary activation by employing a combinationof the solid product (III) with an organoaluminum compound (A₂), areaction product (G) of an organoaluminum compound (A₃) with an electronacceptor (B₃), and an α-olefin (F) will be mentioned below in detail.

The organoaluminum compounds (A₁), (A₂) and (A₃) may be the same ordifferent. The most preferable (A₁), (A₂) and (A₃) are dialkylaluminumhalides, dialkylaluminum halides and trialkylaluminums, respectively.

As for the α-olefin (F) employed for the preliminary activation,straight chain monoolefins such as ethylene, propylene, butene-1,hexene-1, heptene-1 and branched chain monoolefins such as4-methyl-pentene-1, 2-methyl-pentene-1, 3-methyl-butene-1, and styrene,etc. are mentioned. These olefins may be the same as or different fromα-olefins employed for polymerization, and may be employed in admixture.

The electron donor (B₃) employed for preparing the reaction product (G)is the same as those described in the reaction for obtaining the solidproduct (III), but is not necessary to be the same as that employed forobtaining the solid product (III). The reaction product (G) is usuallyobtained by reacting 1 mol of an organoaluminum compound with 0.01 to 5mols of an electron donor in the presence of a solvent such as n-hexane,n-heptane, in an amount of 10 to 5,000 ml based on 1 g of theorgano-aluminum and based on 1 g of the electron donor, at -30° to 100°C. for 10 minutes to 3 hours. Usually, the reaction is carried out bydropwise adding the electron donor diluted with the solvent to theorganoaluminum compound diluted with the solvent.

The preliminary activation may be carried out in a hydrocarbon solventsuch as propane, butane, n-pentane, n-hexane, n-heptane, benzene,toluene, or in a liquefied α-olefin such as liquefied propylene,liquefied butene-1, or in an α-olefin gas such as ethylene gas,propylene gas. Further, hydrogen may be made coexistent in thepreliminary activation.

The preliminary activation may be carried out by subjecting a part orthe whole of the catalyst components of 1 g of the solid product (III),0.1 to 500 g, preferably 0.5 to 50 g of an organoaluminum compound and0.05 to 10 g of the reaction product (G), to polymerization treatment atleast in the presence of the solid product (III) and the organoaluminumcompound, with 0.01 to 5,000 g of an α-olefin. As for the conditions ofthe polymerization treatment, it is preferable that the temperature bein the range of 0° to 100° C., preferably 10° to 70° C., the time be inthe range of one minute to 20 hours, and the α-olefin be polymerized inan amount of 0.01 to 2,000 g, preferably 0.05 to 200 g per g of thesolid product (III). In the polymerization treatment, 10 l or less ofhydrogen may be made present. In the preliminary activation, 50 l orless of a solvent may be employed.

In advance of the preliminary activation, polymer particles obtained byslurry, bulk or gas phase polymerization may be made coexistent. Suchpolymer may be the same as or different from α-olefin polymers as theobject of polymerization. The amount of such polymer capable of beingmade coexistent may be in the range of 0 to 5,000 g per g of the solidproduct (III).

The solvent or α-olefin employed in the preliminary activation may beremoved by distilling off, filtration or the like means, midway duringthe preliminary activation or after completion of the activation.Further, for suspending the solid product in a solvent of 80 l or lessper g of the solid product, the solvent may be added.

For the preliminary activation, there are various methods. As for themain embodiments therefor, the following are illustrated:

(1) a method wherein solid product (III) is combined with organoaluminumcompound (A₂), and α-olefin (F) is added to carry out polymerizationtreatment, followed by adding reaction product (G);

(2) a method wherein solid product (III) is combined with (A₂) in thepresence of (F) to carry out polymerization treatment with (F), followedby adding (G);

(3) a method wherein solid product (III) is combined with (A₂), and (G)is added, followed by polymerization treatment with (F); and

(4) a method wherein, after the procedure of the above (3), (G) isfurther added.

With regard to the methods (1) and (2) of preliminary activation, thefollowing concrete methods are further illustrated:

(1-1) a method wherein solid product (III) is combined with (A₂) and theresulting combination is subjected to polymerization treatment with (F)in vapor phase or in liquefied α-olefin or in a solvent, followed byremoving unreacted (F) or unreacted (F) and solvent and thereafteradding (G);

(1-2) a method wherein (G) is added without removing unreacted (F) orunreacted (F) and solvent, in (1-1);

(1-3) a method wherein (G) is added and thereafter unreacted (F) orunreacted (F) and solvent are removed, in (1-2);

(1-4) a method according to 1-1)-(1-3) wherein αolefin polymer obtainedin advance is added;

(1-5) a method according to (1-1)-(1-4) wherein after preliminaryactivation, solvent or unreacted (F) and solvent are removed to obtain acatalyst in the form of powder;

(2-1) a method wherein (A₂) is combined with solid product (III) in thepresence of propylene dissolved in a solvent or liquefied α-olefin orα-olefin gas, to carry out polymerization treatment with α-olefin,followed by adding (G);

(2-2) a method wherein (2-1) is carried out in the presence of α-olefinpolymer obtained in advance; and

(2-3) a method wherein after preliminary activation, unreacted (F) andsolvent are removed under reduced pressure to obtain a catalyst in theform of powder.

In the methods (1) and (2), it is possible that a component obtained bysubjecting a combination of solid product (III) with (A₂) topolymerization treatment with (F) is not mixed with (G) at the time ofcatalyst preparation, but they are mixed together just beforepolymerization. Further, in the methods (1)-(4), it is possible toemploy hydrogen together with (F). Whether the catalyst is prepared inthe form of slurry or in the form of powder affords no essentialdifference.

The preliminarily activated catalyst prepared as mentioned above isemployed for producing α-olefin polymers. The polymerization may becarried out either by slurry polymerization in a hydrocarbon solvent orby bulk polymerization in liquefied α-olefin monomer, but, in thepresent invention, since the catalyst has a high activity, gas phasepolymerization of α-olefins exhibits a particularly notableeffectiveness, and slurry or bulk polymerization followed by gas phasepolymerization as a modification of gas phase polymerization alsoexhibits a desirable effectiveness.

The gas phase polymerization of α-olefins may be carried out not only inthe absence of solvent such as n-hexane, n-heptane, but also in a statewhere 0 to 500 g of solvent per Kg of α-olefin polymer is contained.Further it may be carried out either by continuous polymerization orbatch polymerization. Furthermore, it may be carried out in fluidizedbed manner, or in fluidized manner by way of agitating elements, or instirring manner by way of vertical or horizontal type paddle.

As for the method of slurry or bulk polymerization followed by gas phasepolymerization, of α-olefins, the following are illustrated: forexample, in the case of batch polymerization, a method wherein α-olefinis polymerized in a solvent or liquefied α-olefin monomer, andthereafter the solvent or α-olefin monomer is removed so that it iscontained in an amount of 500 g or less per Kg of polymer particles,followed by polymerizing α-olefin in vapor phase, and a method whereinpolymerization of α-olefin is continued without removing the solvent orliquefied α-olefin, and moves into gas phase polymerization withoutadding any operation since the solvent or liquefied α-olefin is absorbedin the resulting polymer. A plural step polymerization consisting of acombination of slurry or bulk polymerization with gas phasepolymerization exhibits a desirable result particularly in the case ofcontinuous polymerization. This plural step polymerization may becarried out as follows: In the first step, slurry or bulk polymerizationis carried out wherein the polymerization is continued so as to give aslurry concentration [(polymer (Kg))/(polymer (Kg)+solvent or liquefiedα-olefin (Kg))+100%[ of 70% or higher, or the polymerization is carriedout until a slurry concentration reaches 30 to 50%, and thereaftersolvent or liquefied α-olefin is removed so as to give a slurryconcentration of 70% or higher; and in the second step, α-olefin issubjected to vapor phase polymerization. In this method, the catalyst isadded at the time of slurry or bulk polymerization of the first step,and in the gas phase polymerization successively carried out, thecatalyst of the first step may be sufficiently employed as it is, but afresh catalyst may be also added in the second step. As for theproportion of the weight of polymer formed by slurry or bulkpolymerization and that of polymer formed by gas phase polymerization,it is preferable that the proportion be in the range of 0.1 to 100 partsby weight of polymer of gas phase polymerization based on one part ofpolymer of slurry or bulk polymerization.

The stereoregularity of polymer is controlled by varying the molar ratioof electron donor (B₃) to organoaluminum (A₃), of reaction product (G)(which will be hereinafter referred to as (G) molar ratio). The molarratio is varied in the range of 0.01 to 5. Lower molar ratio results inlower stereoregularity, while higher molar ratio results in higherstereoregularity.

As for the polymerization conditions of α-olefins, any of slurrypolymerization, bulk polymerization and gas phase polymerization may becarried out at a polymerization temperature of room temperature (20° C.)to 200° C., under a polymerization pressure of the atmospheric pressure(0 kg/cm² G) to 50 kg/cm² G and usually for 5 minutes to 10 hours. Inthe polymerization, addition of a suitable amount of hydrogen foradjustment of molecular weight, and the like means are carried out as inconventional manner.

As for the α-olefins employed in the polymerization of the presentinvention, straight chain monoolefins such as ethylene, propylene,butene-1, hexene-1, octene-1, etc., branched chain monoolefins such as4-methyl-pentene-1, 2-methyl-pentene-1, 3-methyl-butene-1, etc.,diolefins such as butadiene, isoprene, chloroprene, etc., styrene, etc.are mentioned. These olefins may be homopolymerized or copolymerized incombination with each other, for example, in combination of propylenewith ethylene; butene with ethylene; and propylene with butene-1. Inthis case, they may be polymerized in admixture of monomers or in aplurality of steps where different α-olefins may be employed in thefirst step slurry or bulk polymerization and the second step gas phasepolymerization.

The main effectiveness of the present invention consists in that even inthe case of gas phase polymerization process where the monomerconcentration is relatively low, a highly crystalline polymer having agood form of powder can be obtained with a high polymer yield, and alsothe stereo-regularity of polymer can be optionally controlled.

The effectiveness of the present invention will be further described inmore detail.

The first effectiveness of the present invention is that the activity ofthe catalyst obtained is so high that a high polymer yield is, ofcourse, obtained not only in the case of slurry or bulk polymerization,but also even in the case of gas phase polymerization where the monomerconcentration is relatively low, that is, the polymer yield per g ofsolid product (III) in the case of gas phase polymerization amounts to7,000 to 12,000 g (polymer).

The second effectiveness of the present invention is that since thepolymer is obtained with a high yield, even if the amounts of alcohol,alkylene oxide, steam, etc. employed for killing the catalyst afterproduction of α-olefin polymers or purifying the polymer are furtherreduced, polymer is not colored and has a yellowness index (YI) as lowas 0 to 2.0; further, evolution of corrosive gas having a bad effectsuch as degradation of physical properties of polymer or rusting of moldat the time of molding of polymer does not occur: for example, even inthe case where polymer is heated at 200° C., evolution of acidic gaschanging the color of a testing paper of Congo Red is not observed.

The third effectiveness of the present invention is that the percentageof amorphous polymer formed at the time of production of α-olefinpolymers, is reduced, and also such effectiveness is great particularlyat the time of production of copolymer. For example, in the productionof propylene polymer, the amount of isotactic polypropylene asn-hexane-insoluble (20° C.) reaches 98 to 99.8% in terms of isotacticindex, and that of atactic polypropylene as n-hexane-soluble is only 0.2to 2% in terms of atactic index. Thus, even when atactic polymer is notremoved, disadvantages such as degradation of physical properties ofpolymer such as rigidity, heat stability, etc. are overcome, wherebyremoving step of atactic polymer can be omitted, resulting insimplification of production process of polymer.

The fourth effectiveness of the present invention is that it is possibleto control the stereoregularity of polymer without increasing the amountof atactic polymer as n-hexane-soluble. For example, in the case ofpolypropylene, it is possible to optionally control the stereoregularityof homopolymer in the range of 0.88 to 0.96 in terms of absorbancy ratioof those at 995 cm⁻¹ to those at 974 cm⁻¹, measured by infraredabsorption method (which ratio will be hereinafter expressed by IR-τ),and also the stereoregularity of copolymer in the range of 0.83 to 0.95,without increase in the amount of atactic polymer. Heretofore, when thestereoregularity of homopolymer has been reduced, or when copolymershave been produced, for improving the physical properties of moldedproduct of polymer such as rigidity, impact strength, heat sealtemperature, etc., the amount of atactic polymer has increased. Whereasaccording to the present invention, it has become possible to omit theremoving step of atactic polymer and yet optionally control thestereoregularity of polymer depending on the application fields ofpolymer, in the production of polymer.

The fifth effectiveness of the present invention is that it is possibleto optionally control the physical properties, particularly rigidity, ofpolymer in the range of 0.90 to 1.4×10⁴ Kg/cm² in terms of bendingmodulus. Thus it is possible to easily provide polymers suitable forvarious application fields.

The sixth effectiveness of the present invention is that polymerparticles having a good form are obtained and also the average particlesize is small, that is, 90 to 99% of polymer is in a proportion of 32 to60 meshes pass. The form of particles is close to sphere; the amounts oflarge particles and fine particles are reduced; and the particle sizedistiribution is narrow. Further, the bulk density (BD) of polymer is inthe range of 0.45 to 0.52 and a small area of storage tank per unitweight of polymer may be sufficient; hence it is possible to makecompact the plant for producing polymer; neither clogging troublebrought by cohesion of polymer particles nor transporting troublebrought about by fine particles occurs; hence even in the case of gasphase polymerization, it is possible to carry out a long time,stabilized operation.

The seventh effectiveness of the present invention is that storingstability and heat stability of catalyst are both high. Although thiseffectiveness has already been observed in the above-mentioned priorinvention, the effectiveness is maintained as it is, in the presentinvention. For example, even when the solid product (III) is allowed tostand at a high temperature of about 30° C. for about 4 months, no largereduction in the polymerization activity occurs; hence no particularstoring equipment such as that for storing solid product (III) whilecooling it at about 0° C. is necessary, and even when the solid product(III) after combined with an organoaluminum, is allowed to stand in ahigh concentration of the solid product of 1.0% or higher, at 30° C. orhigher, for about one week till polymerization is initiated, finepulverization brought about by agitation in the catalyst tank hardlyoccurs, the form of polymer particles is not degraded, and no reductionin the polymerization activity is observed. This effectiveness isremarkably enhanced by preliminary activation with α-olefin. As aresult, even when the catalyst is stored in the form of powder,reduction in the polymerization activity is small, the form of α-olefinpolymers obtained by employing this catalyst is good; hence the merit ofgas phase polymerization is exhibited.

EXAMPLE 1

(1) Preparation of solid product (III)

n-Hexane (60 ml), diethylaluminum monochloride (DEAC) (0.05 mol) anddiisoamyl ether (0.12 mol) were mixed together at 25° C. for one minuteand then reacted at the same temperature for 5 minutes, to obtain areaction liquid (I) (molar ratio of diisoamyl ether/DEAC:2.4). TiCl₄(0.4 mol) was introduced into a reactor purged with nitrogen gas andheated to 35° C., and thereto was dropwise added the total amount of theabove-mentioned reaction liquid (I) for 30 minutes, followed bymaintaining the resulting material at the same temperature for 30minutes, elevating the temperature to 75° C., further reaction for onehour, cooling down to room temperature, removing the supernatant, 4times repeating a procedure of adding 400 ml of n-hexane and removingthe supernatant by decantation, to obtain a solid product (II) (19 g).The total amount of this (II) was suspended in 300 ml of n-hexane, andto the resulting suspension were diisoamyl ether (16 g) and TiCl₄ (35 g)at 20° C. for about one minute, followed by reaction at 65° C. for onehour. After completion of the reaction, the resulting material wascooled down to room temperature (20° C.) and the supernatant was removedby decantation, followed by 5 times repeating a procedure of adding 400ml of n-hexane, stirring for 10 minutes, still standing and removing thesupernatant, and drying under reduced pressure, to obtain a solidproduct (III).

(2) Preparation of preliminarily activated catalyst

A 2 l capacity stainless steel reactor equipped with slant blades waspurged by nitrogen gas, and into this reactor were added n-hexane (20ml), diethylaluminum monochloride (420 mg) and the solid product (III)(30 mg) at room temperature. Thereafter 150 ml of hydrogen wasintroduced, and polymerization treatment was carried out by reactingthem under a partial pressure of propylene of 5 Kg/cm² G for 5 minutes(which polymerization treatment will be hereinafter abbreviated toreaction) (reacted propylene per g of solid product (III): 80.0 g),followed by removing unreacted propylene, hydrogen and n-hexane underreduced pressure, and thereafter adding a reaction product obtained byreaction in n-hexane (20 ml), triethylaluminum (85 mg) andhexamethylphosphoric acid triamide (110 mg) at 35° C. for 30 minutes, toobtain a preliminarily activated catalyst.

(3) Polymerization of propylene

Into the reactor containing the catalyst after completion of thepreliminary activation was introduced 150 ml of hydrogen, and gas phasepolymerization was carried out under a partial pressure of propylene of22 kg/cm² G, at a polymerization temperature of 70° C. for 2 hours.After completion of the reaction, 3 g of methanol was introduced andkilling reaction was carried out at 70° C. for 10 minutes, followed bycooling down to room temperature (20° C.) and drying the resultingpolymer, to obtain 303 g of polymer. The polymer yield per g of solidproduct (III) was 10,100 g, the isotactic index (n-hexane-insoluble at20° C. (%)), 99.0, BD of polymer, 0.48, and the polymer particles wereuniform and no lump was observed. No coloration of polymer was observedand yellowness index (YI) was 0.8. Further, in order to observe theextent of corrosiveness of polymer brought about by the extent of heatstability of catalyst after killing, polymer was heated to a definitetemperature and whether acidic gas is easily or difficultly evolved wasobserved through the presence or absence of color change of Congo Red(according to JIS K-6723). As a result, no color change was observed.

COMPARATIVE EXAMPLE 1

Example 1 was repeated except that, in the preliminary activation ofExample 1, after diethylaluminum monochloride was combined with solidproduct (III), hydrogen was added, followed only by reaction ofpropylene, and no reaction product of triethylaluminum withhexamethylphosphoric acid triamide was added. (Catalyst preparationwhich is different only in no addition of reaction product (G) of anorgano-aluminum compound with an electron donor in the preliminaryactivation, and polymerization by the use of the thus prepared catalyst,as in the case of Comparative example 1 as compared with Example 1, willbe hereinafter referred to as "Polymerization in the case of no additionof reaction product (G) in the corresponding Example" in the followingComparative examples.) The resulting polymerization activity was low.

COMPARATIVE EXAMPLE 2

Example 1 was repeated except that, in the preliminary activation ofExample 1, after diethylaluminum monochloride and solid product (III)were added, reaction product of triethylaluminum withhexamethylphosphoric acid triamide was added without reacting propylene.As a result, polymer lump formed and the polymer yield did not increase.

COMPARATIVE EXAMPLE 3

Example 1 was repeated except that, in the preliminary activation ofExample 1, triethylaluminum was not reacted with hexamethylphosphoricacid triamide, but they were separately added. As a result, thepolymerization activity was low and the isotactic index was also low.

COMPARATIVE EXAMPLE 4

Example 1 was repeated except that, in the formation reaction of thereaction product (I) of Example 1, no diethylaluminum monochloride wasemployed.

COMPARATIVE EXAMPLE 5

Example 1 was repeated except that 0.12 mol (19 g) of diisoamyl ether tobe employed in the formation reaction of solid product (I) of Example 1was not employed, but it was instead added to 16 g of diisoamyl ether tobe employed in the reaction with solid product (II).

COMPARATIVE EXAMPLE 6

Example 1 was repeated except that, in the formation reaction of solidproduct (III) of Example 1, diisoamyl ether was not reacted.

COMPARATIVE EXAMPLE 7

Example 1 was repeated except that a reaction material obtained byadding 0.05 mol of diethylaluminum monochloride to a solution consistingof 0.4 mol of TiCl₄ and 0.12 mol of diisoamyl ether and reacting themtogether, was employed in place of reaction product (II) of Example 1.

COMPARATIVE EXAMPLE 8

Example 1 was repeated except that solid product (II) of Example 1 wasemployed in place of solid product (III).

COMPARATIVE EXAMPLE 9

Example 1 was repeated except that, in the formation reaction of solidproduct (III) of Example 1, TiCl₄ was not employed in the reaction withsolid product (II).

EXAMPLE 2

n-Heptane (80 ml), di-n-butylaluminum monochloride (0.10 mol) anddi-n-butyl ether (0.30 mol) were mixed together at 30° C. for 3 minutes,followed by reaction for 20 minutes to obtain a reaction liquid (I). Thetotal amount of this reaction liquid (I) was dropwise added over 60minutes to a solution consisting of toluene (50 ml) and TiCl₄ (0.64mol), maintained at 45° C. The temperature of the resulting mixture waselevated to 85° C. and reaction was further carried out for 2 hours,followed by cooling down to room temperature, removing the supernatantand twice repeating a procedure of adding 300 ml of n-heptane andremoving the supernatant by decantation to obtain 49 g of solid product(II). The total amount of this (II) was suspended in 300 ml ofn-heptane, and to the resulting suspension were added di-n-butyl ether(20 g) and TiCl₄ (150 g) at room temperature for about 2 minutes,followed by reaction at 90° C. for 2 hours, cooling, decantation,washing with n-heptane and drying to obtain a solid product (III).Thereafter, preliminary activation of catalyst and polymerization ofpropylene were carried out as in Example 1, (2) and (3).

COMPARATIVE EXAMPLE 10

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 2 was carried out.

COMPARATIVE EXAMPLE 11

Example 2 was repeated except that solid product (II) of Example 2 wasemployed in place of solid product (III).

EXAMPLE 3

Example 1 was repeated except that the formation reaction of solidproduct (II) was carried out by dropwise adding reaction liquid (I) toTiCl₄ maintained at 12° C., at 12° C. for 45 minutes, and thereaftermaintaining the resulting mixture at 35° C. for 60 minutes. Theresulting solid product (III) had a brown color.

COMPARATIVE EXAMPLE 12

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 3, was carried out.

EXAMPLE 4

Example 1 was repeated except that, in the formation reaction of solidproduct (II) of Example 1, the elevated temperature 75° C. afterdropwise addition of reaction liquid (I) to TiCl₄, was changed to 65° C.The resulting solid product (III) had a brown color.

COMPARATIVE EXAMPLE 13

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 4 was carried out.

EXAMPLE 5

Diethylaluminum monochloride (0.057 mol) and diisoamyl ether (0.15 mol)were dropwise added to n-hexane (40 ml) at 18° C. for 5 minutes, andreaction was carried out at 35° C. for 30 minutes. The resultingreaction liquid was dropwise added to TiCl₄ (0.5 mol) at 35° C. for 180minutes, followed by further maintaining the resulting mixture at 35° C.for 60 minutes, elevating the temperature to 75° C., heating for 60minutes, cooling down to room temperature (20° C.), removing thesupernatant, and twice repeating a procedure of adding 400 ml ofn-hexane and removing the supernatant by decantation to obtain 24 g of asolid product (II). The total amount of this product was suspended in100 ml of n-hexane, and to the resulting suspension was added 12 g ofdiisoamyl ether, followed by reaction at 35° C., for one hour, addingdiisoamyl ether (12 g) and TiCl₄ (72 g) at 35° C. for 2 minutes,elevating the temperature to 65° C., reaction for one hour, cooling downto room temperature (20° C.), decantation, washing with n-hexane anddrying to obtain a solid product (III). Thereafter, preliminaryactivation and propylene polymerization were carried out as in Example1.

COMPARATIVE EXAMPLE 14

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 5, was carried out.

EXAMPLE 6

Example 5 was repeated except that, in the formation reaction of solidproduct (I), diisopropylaluminum monochloride (0.06 mol) was reactedwith di-n-octyle ether (0.14 mol).

COMPARATIVE EXAMPLE 15

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 6, was carried out.

EXAMPLE 7

Example 5 was repeated except that, in the formation reaction of solidproduct (II) of Example 5, the amount of TiCl₄ empolyed to be reactedwith reaction product (I) was made 0.12 mol.

COMPARATIVE EXAMPLE 16

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 7, was carried out.

EXAMPLE 8

Solid product (II) (24 g) obtained as in Example 5 was suspended in 200ml of toluene, and to the resulting suspension were added TiCl₄ (10 g)and di-n-butyl ether (26 g), followed by reaction at 50° C. for 180minutes, cooling down to room temperature (20° C.), decantation, washingwith n-hexane and drying to obtain solid product (III). Subsequentpreparation of preliminarily activated catalyst and propylenepolymerization were carried out as in Example 1.

COMPARATIVE EXAMPLE 17

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 8, was carried out.

EXAMPLE 9

Triisobutylaluminum (0.03 mol) and di-n-dodecyl ether (0.07 mol) werereacted together in n-hexane (100 ml) at 20° C. for 30 minutes. Theresulting reaction liquid was dropwise added to TiCl₄ (0.15 mol) at 20°C. for 120 minutes, followed by maintaining the resulting mixture at 30°C. for 30 minutes, elevating the temperature to 50° C., reaction for 60minutes, decantation of the supernatant, washing with n-hexane anddrying to obtain a solid product (II) (23 g), which was then suspendedin 50 ml of n-heptane. To the resulting suspension were added di-n-butylether (21 g) and TiCl₄ (40 g), followed by reaction at 50° C. for 140minutes, cooling, decantation of the supernatant, washing with n-hexaneand drying to obtain a solid product (III). The subsequent preparationof preliminarily activated catalyst and propylene polymerization werecarried out as in Example 1.

COMPARATIVE EXAMPLE 18

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 9, was carried out.

The results of Examples 1 to 9 and Comparative Examples 1 to 18 areshown in Table 1.

The terms "solid catalyst component" in this Table refer collectively tosolid product (III), and solid product corresponding to solid product(III) as well as solid product (II) combined with organoaluminum, etc.and employed for polymerization in Comparative examples. This definitionalso applies to the succeeding Tables.

                                      TABLE 1                                     __________________________________________________________________________          Polymer yield            Proportion                                           per g of solid           of 32 ˜ 60                                                                    4 Meshes                                                                           Congo Red test.sup.3                      catalyst                                                                              Isotactic   Polymer                                                                            meshes pass                                                                         on   (time till color                    No.   component (g)                                                                         index                                                                              MFR.sup.1                                                                         YI.sup.2                                                                         BD   (%)   (%)  change)                             __________________________________________________________________________    Example 1                                                                           10,100  99.0 3.8 0.8                                                                              0.8  98.0  0    unchanged                           Compara-                                                                      tive ex. 1                                                                          5,100   99.1 3.6 3.0                                                                              0.48 96.3  0    1 min.                              Compara-                                                                      tive ex. 2                                                                          2,200   99.0 3.8 7.4                                                                              0.31 12.0  14.0 30 sec.                             Compara-                                                                      tive ex. 3                                                                          5,300   89.0 3.6 3.5                                                                              0.42 90.0  0    2 min.                              Compara-                                                                      tive ex. 4                                                                          160     96.5 4.3 >20                                                                              0.25 50.0  48   5 sec.                              Compara-                                                                      tive ex. 5                                                                          110     --   --  -- --   --    --   --                                  Compara-                                                                      tive ex. 6                                                                          3,000   98.0 4.1 7.6                                                                              0.40 49.0  18   1 min.                              Compara-                                                                      tive ex. 7                                                                          2,600   96.0 4.3 6.8                                                                              0.40 55.0  14   40 sec.                             Compara-                                                                      tive ex. 8                                                                          1,800   98.5 3.9 15.0                                                                             0.42 58.0  25   30 sec.                             Compara-                                                                      tive ex. 9                                                                          3,400   95.0 4.4 4.8                                                                              0.40 80.0  12   1 min.                              Example 2                                                                           11,000  99.1 4.2 0.6                                                                              0.50 98.5  0    unchanged                           Compara-                                                                      tive ex. 10                                                                         4,500   99.0 3.6 3.8                                                                              0.49 94.6  0    1 min.                              Compara-                                                                      tive ex. 11                                                                         3,300   98.4 4.1 5.6                                                                              0.40 79.0  18   "                                   Example 3                                                                           11,300  99.0 4.1 0.5                                                                              0.50 98.5  0    unchanged                           Compara-                                                                      tive ex. 12                                                                         4,400   99.1 4.2 3.7                                                                              0.49 96.5  0    1 min.                              Example 4                                                                           10,780  98.5 3.1 0.6                                                                              0.49 97.0  0    unchanged                           Compara-                                                                      tive ex. 13                                                                         4.200   98.5 4.1 4.0                                                                              0.49 98.0  0    50 sec.                             Example 5                                                                           11,900  99.0 3.6 0.4                                                                              0.50 97.6  0    unchanged                           Compara-                                                                      tive ex. 14                                                                         5,100   99.0 3.8 3.1                                                                              0.49 96.7  0    1 min.                              Example 6                                                                           10,500  98.6 3.1 0.8                                                                              0.50 98.6  0    unchanged                           Compara-                                                                      tive ex. 15                                                                         4.200   98.4 3.6 4.0                                                                              0.46 90.0  0    40 sec.                             Example 7                                                                           11,800  99.1 3.8 0.4                                                                              0.50 97.0  0    unchanged                           Compara-                                                                      tive ex. 16                                                                         4,900   99.0 3.1 3.2                                                                              0.48 95.0  0    1 min.                              Example 8                                                                           10,100  99.0 3.8 0.6                                                                              0.50 96.0  0    unchanged                           Compara-                                                                      tive ex. 17                                                                         4,700   99.0 3.3 3.5                                                                              0.49 93.2  0    1 min.                              Example 9                                                                           10,800  98.7 4.1 0.7                                                                              0.48 96.0  0    unchanged                           Compara-                                                                      tive ex. 18                                                                         4,200   98.6 3.6 4.0                                                                              0.45 92.0  0    30 sec.                             __________________________________________________________________________     Note-                                                                         .sup.1 Melt flow rate (according to ASTM                                      .sup.2 Yellowness index (according to JIS                                     .sup.3 According to JIS K6723                                            

EXAMPLE 10

n-Pentane (4 ml), diethylaluminum monochloride (160 mg), solid product(III) (32 mg) obtained in Example 1 and polypropylene powder (5 g) wereintroduced and mixed together, followed by removing n-pentane underreduced pressure. While the resulting material was fluidized withpropylene gas under a partial pressure of propylene of 0.8 Kg/cm² G, at30° C. for 20 minutes, propylene was reacted in gas phase (reactedpropylene per g of solid product (III): 1.8 g) followed by purgingunreacted propylene, and adding a reaction product (G) obtained byreacting triethylaluminum (30 mg) with ethyl benzoate (41 mg) inn-pentane (10 ml) at 20° C. for 10 minutes to obtain a preliminarilyactivated catalyst. Thereafter gas phase polymerization of propylene wascarried out as in Example 1, (3).

COMPARATIVE EXAMPLE 19

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 10 was carried out.

EXAMPLE 11

Di-n-butylaluminum monochloride (120 mg) and solid product (III) (25 mg)obtained in Example 2 were introduced into propylene (30 g), followed byreaction under 9.8 Kg/cm² G for 10 minutes (reacted propylene per g ofsolid product (III): 120 g). After purging unreacted propylene, areaction product (G) obtained by reacting triisobutylaluminum (54 mg)with ethyl benzoate (30 mg) in n-hexane (18 ml) at 30° C. for 30 minuteswas added to obtain a preliminarily activated catalyst. Thereafter gasphase polymerization of propylene was carried out as in Example 1, (3).

COMPARATIVE EXAMPLE 20

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 11 was carried out.

EXAMPLE 12

Diethylaluminum monochloride (280 mg) and solid product (III) (25 mg)obtained in Example 2 were introduced into n-pentane (20 ml).Thereafter, while the partial pressure of propylene was elevated up to 5Kg/cm² G at 15° C. (rate of pressure elevation: 1 Kg/cm² G/min.),propylene was reacted (reacted propylene per g of solid product (III):3.2 g). After purging unreacted propylene, a reaction product (G)obtained by reacting triethylaluminum (23 mg) with methyl p-toluylate(18 mg) in n-pentane (20 ml) at 15° C. for 30 minutes was added toobtain a preliminarily activated catalyst. Thereafter gas phasepolymerization of propylene was carried out as in Example 1, (3).

COMPARATIVE EXAMPLE 21

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 12 was carried out.

EXAMPLE 13-15

Example 12 was repeated except that, in the preliminary activation ofcatalyst of Example 12, the following reaction products (G) wereemployed in place of reaction product of triethylaluminum with methylp-toluylate:

EXAMPLE 13

Reaction product of triisobutylaluminum (84 mg) withN,N,N',N'-tetramethylhexaethylenediamine (90 mg)

EXAMPLE 14

Reaction product of diethylaluminum monochloride (24 mg),triethylaluminum (40 mg) and ethyl p-anisate (36 mg)

EXAMPLE 15

Reaction product of ethylaluminum dichloride (25 mg), triethylaluminum(75 mg) and N,N,N',N'-tetramethylurea (28 mg)

EXAMPLE 16

Example 12 was repeated except that, in the preparation of reactionproduct (G), diphenyl ether (34 mg) was employed in place of methylp-toluylate.

EXAMPLE 17

n-Hexane (10 ml), diethylaluminum monochloride (210 mg) and solidproduct (III) (28 mg) obtained in Example 1 were introduced, and furthera reaction product (G) obtained by reacting triethylaluminum (11 mg)with ethyl benzoate (15 mg) in n-hexane (20 ml) at 28° C. for 30 minuteswas added, followed by removing n-hexane under reduced pressure. Whilethe resulting material was fluidized with propylene under a partialpressure of propylene of 2 Kg/cm² G at 30° C. for 10 minutes, reactionwas carried out in gas phase to obtain a preliminarily activatedcatalyst, followed by carrying out gas phase polymerization of propyleneas in Example 1, (3).

COMPARATIVE EXAMPLE 22

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 17 was carried out.

EXAMPLE 18

Propylene was in advance dissolved in n-hexane (100 ml) under a partialpressure of propylene of 2 Kg/cm² G at 50° C., and into the resultingsolution were added diethylaluminum monochloride (180 mg), solid product(III) (20 mg) obtained in Example 1 and a reaction product (G) obtainedby reacting triisobutylaluminum (18 mg) with methyl p-toluylate (24 mg)in n-hexane (10 ml) at 20° C. for one hour, followed by maintaining thepartial pressure of propylene for 7 minutes so as to give 20 g ofreacted propylene per g of solid product (III), purging unreactedpropylene and removing n-hexane under reduced pressure. Thereafter gasphase polymerization of propylene was carried out as in Example 1, (3).

COMPARATIVE EXAMPLE 23

Polymerization in the case of no addition of reaction product (G) in thecorresponding Example 18 was carried out.

EXAMPLE 19

Example 1 was repeated except that, in the preparation of preliminarilyactivated catalyst of Example 1, ethylene was reacted in place ofpropylene, under 1 Kg/cm² G, at 35° C. for 10 minutes (reacted ethyleneper g of solid produce (III): 2.4 g).

EXAMPLE 20

Example 1 was repeated except that, in the preparation of preliminarilyactivated catalyst of Example 1, butene-1 was reacted in place ofpropylene, under 0.5 Kg/cm² G at 35° C. for 10 minutes (reacted butene-1per g of solid product (III): 0.3 g).

EXAMPLE 21

Example 1 was repeated except that diisopropylaluminum monochloride (380mg) was employed in place of diethylaluminum monochloride, in Example 1,(2).

The results of Examples 10-21 and Comparative examples 19-23 are shownin Table 2.

                                      TABLE 2                                     __________________________________________________________________________          Polymer yield           Proportion                                            per g of solid          of 32 ˜ 60                                                                    4 Meshes                                                                           Congo Red test                             catalyst                                                                              Isotactic  Polymer                                                                            meshes pass                                                                         on   (time till color                     No.   component (g)                                                                         index                                                                              MFR YI                                                                              BD   (%)   (%)  change)                              __________________________________________________________________________    Example 10                                                                          11,300  99.4 3.2 0.5                                                                             0.49 97.6  0    No color change                      Compara-                                                                      tive ex. 19                                                                         5,100   99.3 4.3 2.9                                                                             0.48 90.8  0    1 min.                               Example 11                                                                          10,900  99.0 3.6 0.8                                                                             0.49 92.5  0    No color change                      Compara-                                                                      tive ex. 20                                                                         5,000   99.0 3.8 2.8                                                                             0.46 92.5  0    1 min.                               Example 12                                                                          9,800   99.5 4.1 1.2                                                                             0.48 97.4  0    No color change                      Compara-                                                                      tive ex. 21                                                                         4,600   98.8 3.4 3.5                                                                             0.49 93.0  0    1 min.                               Example 13                                                                          9,600   98.9 3.2 1.4                                                                             0.49 96.0  0    No color change                      Example 14                                                                          9,200   98.9 4.1 1.3                                                                             0.48 95.6  0    "                                    Example 15                                                                          9,100   99.0 4.2 1.4                                                                             0.49 97.4  0    "                                    Example 16                                                                          9,000   98.5 4.1 1.6                                                                             0.48 96.0  0    "                                    Example 17                                                                          9,900   99.1 4.2 1.0                                                                             0.49 95.3  0    "                                    Compara-                                                                      tive ex. 22                                                                         4,900   98.9 4.1 3.4                                                                             0.49 92.0  0    1 min.                               Example 18                                                                          9,950   99.0 4.3 1.1                                                                             0.49 96.8  0    No color change                      Compara-                                                                      tive ex. 23                                                                         5,100   98.9 4.3 3.1                                                                             0.49 93.0  0    1 min.                               Example 19                                                                          9,100   98.5 3.2 1.1                                                                             0.46 92.0  0    No color change                      Example 20                                                                          9,400   98.8 3.6 1.0                                                                             0.47 96.0  0    "                                    Example 21                                                                          9,900   99.1 3.4 0.6                                                                             0.48 96.0  0    "                                    __________________________________________________________________________

EXAMPLE 22

After a preliminarily activated catalyst was obtained as in Example 12,300 ml of hydrogen and then 600 g of propylene were introduced, and bulkpolymerization was carried out at 70° C. under a partial pressure ofpropylene of 31 Kg/cm² g, for 2 hours. After completion of the reaction,unreacted propylene was purged and post-treatment was carried out as inExample 1 to obtain a polymer.

EXAMPLE 23

After a preliminarily activated catalyst was obtained as in Example 12,300 ml of hydrogen and then 200 g of propylene were introduced, and bulkpolymerization was carried out at 60° C., under a partial pressure ofpropylene of 26 Kg/cm² G for 30 minutes to polymerize 35 g of propylene.Thereafter, while the resulting slurry containing unreacted propylenewas flushed into a fluidized bed having a diameter of 20 cm and a volumeof 20 l and equipped with agitating elements, and propylene wascirculated at a flow rate of 5 cm/sec. at a reaction temperature of 70°C. under a partial pressure of propylene of 21 Kg/cm² G, to fluidizepolymer, gas phase polymerization was carried out for 2 hours. Thesubsequent post-treatment was carried out as in Example 1.

EXAMPLE 24

Bulk polymerization was carried out under 26 Kg/cm² G, at 60° C. for 30minutes as in Example 23. Thereafter, unreacted liquefied propylene wastransferred to a separate feed tank connected to the reactor, and thetemperature of the reactor was elevated to 72° C. While propylene wasfed from the feed tank to the reactor so as to give a polymerizationpressure of 26 Kg/cm² G, gas phase polymerization was carried out for 2hours. The subsequent post-treatment was carried out as in Example 1.

EXAMPLE 25

Bulk polymerization was carried out under 26 Kg/cm² G at 60° C. for 30minutes as in Example 23. Thereafter, when the polymerizationtemperature was elevated to 70° C., the polymerization pressure became31 Kg/cm² G. When the polymerization was continued as it was, thepressure lowered down to 26 Kg/cm² G during 40 minutes; thus bulkpolymerization moved continuously to gas phase polymerization. Whilepropylene was fed so as to maintain the pressure at 26 Kg/cm² G, gasphase polymerization was carried out for additional 60 minutes. Thesubsequent post-treatment was carried out as in Example 1 to obtain apolymer.

EXAMPLE 26

n-Hexane (1,000 ml), diethylaluminum monochloride (206 mg) and solidproduct (III) (18 mg) obtained in Example 2 were introduced into areactor, and propylene was reacted under a partial pressure of propyleneof 1.2 Kg/cm² G, at 20° C., for 10 minutes (reacted propylene per g ofsolid product (III): 0.6 g). Thereafter, unreacted propylene was purged,and a reaction product (G) obtained by reacting triethylaluminum (23 mg)with methyl p-toluylate (24 mg) in n-hexane (20 ml), at 20° C. for 30minutes, was added to obtain a preliminarily activated catalyst.Thereinto was 150 ml of hydrogen, and slurry polymerization was carriedout under a partial pressure of propylene of 13 Kg/cm² G at 70° C. for 3hours, followed by removing n-hexane by steam stripping to obtain apolymer.

COMPARATIVE EXAMPLE 24

Polymerization in the case of no addition of reaction product (G) inExample 26 was carried out.

EXAMPLE 27

A preliminarily activated catalyst was obtained employing 80 ml ofn-hexane in place of 1,000 ml thereof, in Example 26. Hydrogen (200 ml)was introduced, and slurry polymerization was carried out under apartial pressure of propylene of 10 Kg/cm² G, at 70° C. for 60 minutesto polymerize 60 g of propylene (polymerized propylene per g of solidproduct (III): 3,300 g). The resulting slurry containing solvent andunreacted propylene was introduced into a fluidized bed equipped withagitating elements to carry out gas phase polymerization as in Example23.

EXAMPLE 28

n-Hexane (200 ml), diethylaluminum monochloride (1.8 g) and solidproduct (III) (0.3 g) obtained in Example 2 were introduced into afluidized bed equipped with agitating elements, and propylene wasreacted under a partial pressure of propylene of 1.5 Kg/cm² G, at 25° C.for 10 minutes (reacted propylene per g of solid product (III): 1.1 g).Further, a reaction product (G) obtained by reacting triethylaluminum(0.45 g) with methyl p-toluylate (0.36 g) in n-hexane (80 ml) at 20° C.for 5 hours was added to obtain a preliminarily activated catalyst.Hydrogen (3,000 ml) was introduced, and propylene was reacted under apartial pressure of propylene of 21 Kg/cm² G at 70° C. under itscirculation at a rate of 5 cm/sec. Initially slurry polymerization wascarried out, but after one hour (polymerized propylene per g of solidproduct (III): 5,200 g), polymer began to cause fluidization, and gasphase polymerization was carried out for additional one hour. Afterpolymerization, post-treatment was carried out as in Example 1 to obtaina polymer.

COMPARATIVE EXAMPLE 25

Polymerization in the case of no addition of reaction product (G) inExample 28 was carried out.

EXAMPLE 29

Solid product (III) obtained as in Example 1 was stored at 30° C. for 4months. Thereafter, propylene was polymerized as in Example 1 (2) and(3).

EXAMPLE 30

A preliminarily activated catalyst obtained as in Example 12 was allowedto stand with stirring at 30° C. for one week, followed by polymerizingpropylene as in Example 12.

COMPARATIVE EXAMPLE 26

Catalyst preparation was carried out as in Example 12 except that afterdiethylaluminum monochloride and solid product (III) were introducedinto n-pentane, propylene was not reacted. Thereafter the catalyst wasallowed to stand with stirring at 30° C. for one week, followed bypolymerizing propylene as in Example 12. Polymerization activity wasnotably reduced; also polymer BD was reduced; and polymer lump formed.

The results of Examples 22-30 and Comparative examples 24-26 are shownin Table 3.

                                      TABLE 3                                     __________________________________________________________________________          Polymer yield           Proportion                                            per g of solid          of 32 ˜ 60                                                                    4 Meshes                                                                           Congo Red test                             catalyst                                                                              Isotactic  Polymer                                                                            meshes pass                                                                         on   (time till color                     No.   component (g)                                                                         index                                                                              MFR YI                                                                              BD   (%)   (%)  change)                              __________________________________________________________________________    Example 22                                                                          10,200  99.0 3.8 0.4                                                                             0.48 97.0  0    No color change                      Example 23                                                                          11,000  98.8 3.2 0.3                                                                             0.49 96.8  0    "                                    Example 24                                                                          10,800  98.9 2.6 0.4                                                                             0.48 93.0  0    "                                    Example 25                                                                          10,600  98.9 3.8 0.6                                                                             0.49 96.0  0    "                                    Example 26                                                                          8,800   99.3 4.1 1.4                                                                             0.50 97.4  0    "                                    Compara-                                                                      tive ex. 24                                                                         4,200   99.0 4.4 4.0                                                                             0.48 92.0  0    30 sec.                              Example 27                                                                          9,900   99.4 3.8 1.0                                                                             0.49 96.8  0    No color change                      Example 28                                                                          10,050  99.6 4.2 0.4                                                                             0.50 96.9  0    "                                    Compara-                                                                      tive ex. 25                                                                         5,100   99.0 4.2 3.2                                                                             0.49 95.0  0    1 min.                               Example 29                                                                          8,800   99.0 3.2 1.2                                                                             0.48 97.6  0    No color change                      Example 30                                                                          8,100   99.0 3.1 1.6                                                                             0.46 93.0  0    "                                    Compara-                                                                      tive ex. 26                                                                         2,430   92.0 4.5 16                                                                              0.21 10.0  25   30 sec.                              __________________________________________________________________________

EXAMPLE 31

Employing the catalyst obtained in Example 1, ethylene polymerizationwas carried out under a partial pressure of hydrogene of 12 Kg/cm² G anda partial pressure of ethylene of 12 Kg/cm² G, at 85° C.

EXAMPLE 32

A polymer (propylene-ethylene block copolymer) was obtained as inExample 27 except that the slurry polymerization of the first step wascarried out with propylene, and the gas phase polymerization of thesecond step was carried out with ethylene under a partial pressure ofhydrogen of 8 Kg/cm² and a partial pressure of ethylene of 12 Kg/cm² Gat 70° C. for 2 hours.

EXAMPLE 33

A polymer (propylene-ethylene copolymer) was obtained as in Example 23except that an olefin mixture of 200 g of propylene with 20 g ofethylene was employed in place of 200 g of propylene.

EXAMPLE 34

A polymer (propylene-butene-1 copolymer) was obtained as in Example 33except that 30 g of butene-1 was employed in place of 20 g of ethylene.

EXAMPLE 35

Employing a preliminarily activated catalyst obtained as in Example 1,(1) and (2) except that 320 mg of triethylaluminum was employed in placeof diethylaluminum monochloride in Example 1 (2), ethylenepolymerization was carried out as in Example 31.

EXAMPLE 36

Diethylaluminum monochloride (941 mg), solid product (III) 480 mg)obtained in Example 1 and a reaction product (G) (132 mg) ((G) molarratio:0.30) obtained by reacting triethylaluminum (95 mg) (0.83 mmol)with methyl p-toluylate (37 mg) (0.25 mmol) in n-hexane (300 ml) at 28°C. for one hour, were added to n-hexane (500 ml), and propylene wasreacted under a partial pressure of propylene of 2 Kg/cm² G at 35° C.for 10 minutes (reacted propylene per g of solid product (III): 17 g),followed by purging unreacted propylene to obtain a preliminarilyactivated catalyst. Successively, 3,900 ml of hydrogen was introduced,and while ethylene was fed at a rate of 1.6 g/min. under a partialpressure of propylene of 22 Kg/cm² G, propylene-ethylenecopolymerization was carried out at 60° C. for 120 minutes. Ethylenecontent in the polymer was 3.4%.

COMPARATIVE EXAMPLE 27

Polymerization in the case of no addition of reaction product (G) inExample 36 was carried out.

COMPARATIVE EXAMPLES 28-30

Example 36 was repeated except that, in the preliminary activation ofExample 36, triethylaluminum (95 mg) (0.83 mmol) (Comparative example28) or methyl p-toluylate (37 mg) (0.25 mmol) (Comparative example 29)was employed in place of reaction product (G), or triethylaluminum (95mg) was not reacted with methyl p-toluylate (37 mg), but they wereseparately and at the same time added (Comparative example 30). In anyof these cases, atactic polymer increased.

COMPARATIVE EXAMPLE 31

Example 36 was repeated except that, in the preparation of thepreliminarily activated catalyst, no propylene was reacted. Polymer lumpformed and polymer yield did not increase.

EXAMPLE 37

Example 36 was repeated except that ethylene was fed at a rate of 2.3g/min. Ethylene content in polymer was 5.1%.

The results of Examples 31 and 37 and Comparative examples 27-31 areshown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________          Polymer yield                                                                         Ethylene              Proportion                                                                          4   Congo Red                             per g of solid                                                                        content               of 32 ˜ 60                                                                    Meshes                                                                            test (time                            catalyst                                                                              in polymer                                                                          Isotactic  Polymer                                                                            meshes pass                                                                         on  till color                      No.   component (g)                                                                         (%)   index                                                                              MFR YI                                                                              BD   (%)   (%) change)                         __________________________________________________________________________    Example 31                                                                          8,300         --   2.6 1.8                                                                             0.46 90.0  0   No color                                                                      change                          Example 32                                                                          10,100        98.5 3.6 0.6                                                                             0.49 93.0  0   No color                                                                      change                          Example 33                                                                          11,200        98.5 3.1 0.3                                                                             0.50 93.4  0   No color                                                                      change                          Example 34                                                                          11,300        98.8 3.2 0.4                                                                             0.48 93.6  0   No color                                                                      change                          Example 35                                                                          9,200         --   2.8 0.9                                                                             0.47 97.0  0   No color                                                                      change                          Example 36                                                                          11,000  3.4   98.5 4.1 0.4                                                                             0.46 96.0  0   No color                                                                      change                          Compara-                                                                      tive ex. 27                                                                         5,100   3.3   97.8 4.0 3.0                                                                             0.42 92.0  0   one min.                        Compara-                                                                      tive ex. 28                                                                         5,800   3.2   84.0 4.1 3.2                                                                             0.21 12.0  12  "                               Compara-                                                                      tive ex. 29                                                                         4,200   3.4   94.0 4.2 4.1                                                                             0.42 95.0  0   "                               Compara-                                                                      tive ex. 30                                                                         4,100   3.5   90.0 4.1 4.4                                                                             0.35 22.0  8   "                               Compara-                                                                      tive ex. 31                                                                         2,200   3.6   92.0 4.1 8.9                                                                             0.28 18.0  14  30 sec.                         Example 37                                                                          10,800  5.1   98.0 4.1 0.2                                                                             0.42 96.0  0   No color                                                                      change                          __________________________________________________________________________

EXAMPLE 38

Triethylaluminum (0.07 mol) was mixed with di-n-propyl ether (0.15 mol)in n-octane (45 ml) at 20° C. for 2 minutes and then they were reactedtogether at the same temperature for 30 minutes to obtain a solidproduct (I), which was then dropwise added to TiCl₄ (0.6 mol) at 32° C.over 4 hours, followed by maintaining the temperature at 35° C. for onehour, further elevating the temperature to 78° C., reacting for 2 hours,cooling down to room temperature (20° C.), removing the supernatant, 5times repeating a procedure of adding 400 ml of n-hexane and removingthe supernatant by decantation, confirming that TiCl₄ was not detectedin the decanted liquid, filtration and drying to obtain 23 g of a solidproduct (II).

Di-n-pentyl ether (47 ml) and anhydrous AlCl₃ (5 g) were added ton-heptane (300 ml) and they were reacted together at 80° C. for 2 hoursto dissolve anhydrous AlCl₃, followed by cooling down to 30° C., addingthe above-mentioned solid product (II) (23 g), reaction at 80° C., for 2hours, cooling down to room temperature, removing the supernatant bydecantation, 3 times repeating a procedure of adding 300 ml of n-hexaneand removing the supernatant by decantation, filtration and drying toobtain a solid product (III). The subsequent preliminary activation ofcatalyst and propylene polymerization were carried out as in Example 1,(2) and (3).

EXAMPLE 39

In place of the reaction of reaction product (II) with diisoamyl etherand TiCl₄ in Example 1, diisoamyl ether (38 g), SiCl₄ (12 g) and TiCl₄(17 g) were added to n-hexane (200 ml) at room temperature (20° C.) forabout one minute, followed by adding solid product (II) (19 g), reactionat 75° C. for 2 hours, washing with n-hexane and drying to obtain asolid product (III). The subsequent preliminary activation of catalystand propylene polymerization were carried out as in Example 1, (2) and(3).

COMPARATIVE EXAMPLE 31

Example 1 was repeated except that, in the preparation of solid product(III), after the reaction of TiCl₄ with reaction product (I), thesupernatant was not removed, but n-hexane was added so as to give 300ml, and the resulting liquid was employed in place of the suspension ofsolid product (II), for the subsequent reaction with diisoamyl ether andTiCl₄.

COMPARATIVE EXAMPLE 32

Example 1 was repeated except that, in the preparation of solid product(III) of Example 1, n-hexane (60 ml) and diethylaluminum monochloride(0.05 mol) were added to a solution consisting of TiCl₄ (0.4 mol) anddiisoamyl ether (0.12 mol), at 35° C. for 30 minutes, followed bymaintaining the temperature at the same one for 30 minutes, elevatingthe temperature to 75° C., reaction for additional one hour, coolingdown to room temperature, and washing with n-hexane, to obtain 19 g of asolid product, which was employed in place of solid product (II).

The results of Examples 38 and 39 and Comparative examples 31 and 32 areshown in Table 5.

                                      TABLE 5                                     __________________________________________________________________________           Polymer yield           Proportion                                            per g of solid          of 32 ˜ 60                                                                    4 Meshes                                                                           Congo Red test                             catalyst                                                                              Isotactic  Polymer                                                                            meshes pass                                                                         on   (time till color                    No.    componrnt (g)                                                                         index                                                                              MFR YI                                                                              BD   (%)   (%)  change)                             __________________________________________________________________________    Example 38                                                                           9,800   99.0 3.8 0.6                                                                             0.50 98.0  0    No color change                     Example 39                                                                           10,200  99.0 3.2 0.4                                                                             0.50 96.0  0    "                                   Comparative                                                                   example 31                                                                           3,600   98.0 3.8 5.0                                                                             0.44 50.0  25.0 30 sec.                             Example 32                                                                           4,400   97.8 3.2 4.0                                                                             0.44 55.0  26.0 "                                   __________________________________________________________________________

EXAMPLE 40

Into a stainless steel reactor equipped with slant blades, wereintroduced n-hexane (800 ml), diethylaluminum monochloride (2,880 mg)and solid product (III) (540 mg) obtained in Example 1, at 20° C. andpropylene was reacted under a partial pressure of propylene of 1.5Kg/cm² G at 20° C. for 7 minutes (reacted propylene per g of solidproduct (III): 14 g), followed by purging unreacted propylene, andadding reaction product (G) (419 mg), obtained by reactingtriethylaluminum (181 mg) (1.59 mmol) with methyl p-toluylate (238 mg)(1.59 mmol) ((G) molar ratio: 1.0) in n-hexane (200 ml) at 20° C. for 3hours, to obtain a preliminarily activated catalyst. Successively,hydrogen (7,200 ml) was introduced, and gas phase polymerization wascarried out under a partial pressure of propylene of 22 Kg/cm² G, at apolymerization temperature of 70° C. for 2 hours, followed by adding 48g of methanol, killing reaction at 70° C. for one hour, cooling down toroom temperature (20° C.) and drying to obtain a polymer.

This polymer was pressed at 200° C. under 10 Kg/cm² G for 3 minutes toobtain a film, which was then water-cooled, annealed at 135° C. for 120minutes and subjected to measurement of IR-τ according to Luongo'smethod (see J. P. Luongo, J. Appl. Polymer Sci., 3, 302 (1960)) and alsoto measurement of bending modulus according to JIS K-7203. Further,other measurement values were obtained as in Example 1.

EXAMPLES 41-44

Example 40 was repeated except that the amount of methyl p-toluylateemployed was varied as follows:

    ______________________________________                                        Example 41                                                                            477 mg (3.18 mmol)                                                                            ((G) molar ratio 2.0,                                                         amount of (G) 658 mg)                                 Example 42                                                                            119 mg (0.79 mmol)                                                                            ((G) molar ratio 0.50,                                                        amount of (G) 300 mg)                                 Example 43                                                                            60 mg (0.4 mmol)                                                                              ((G) molar ratio 0.25,                                                        amount of (G) 241 mg)                                 Example 44                                                                             36 mg (0.24 mmol)                                                                            ((G) molar ratio 0.15,                                                        amount of (G) 217 mg)                                 ______________________________________                                    

COMPARATIVE EXAMPLE 33

Example 40 was repeated except that no reaction product (G) wad added inthe catalyst preparation.

COMPARATIVE EXAMPLE 34

Example 40 was repeated except that triethylaluminum (181 mg) (1.59mmol) was employed in place of reaction product (G), in the catalystpreparation. Atactic polymer increased.

COMPARATIVE EXAMPLES 35-39

Example 40 was repeated except that, in the catalyst preparation, thefollowing various amounts of methyl p-toluylate were employed in placeof reaction product (G):

    ______________________________________                                        Comparative ex. 35                                                                            477 mg (3.18 mmol)                                            Comparative ex. 36                                                                            238 mg (1.59 mmol)                                            Comparative ex. 37                                                                            119 mg (0.79 mmol)                                            Comparative ex. 38                                                                            60 mg (0.4 mmol)                                              Comparative ex. 39                                                                             36 mg (0.24 mmol)                                            ______________________________________                                    

IR-τs and bending moduli were unchanged.

The results of Examples 40-44 and Comparative examples 33-39 are shownin Table 6.

                                      TABLE 6                                     __________________________________________________________________________           Polymer yield                      Proportion                                                                          4   Congo Red                        per g of solid  Bending            of 32 ˜ 60                                                                    Meshes                                                                            test (time                       catalyst                                                                              Isotactic                                                                             modulus       Polymer                                                                            meshes pass                                                                         on  till color                No.    component (g)                                                                         index                                                                              IR-τ                                                                         × 10.sup.4 Kg/cm.sup.2                                                         MFR YI BD   (%)   (%) change)                   __________________________________________________________________________    Example 40                                                                           11,300  99.2 0.94                                                                             1.4    4.1 0.4                                                                              0.50 98.0  0   No color                                                                      change                    Example 41                                                                           10,100  99.0 0.96                                                                             1.5    4.2 0.6                                                                              0.50 96.5  0   No color                                                                      change                    Example 42                                                                           11,500  99.5 0.93                                                                             1.3    4.1 0.3                                                                              0.49 98.1  0   No color                                                                      change                    Example 43                                                                           11,700  99.0 0.91                                                                             1.1    4.2 0.2                                                                              0.49 98.2  0   No color                                                                      change                    Example 44                                                                           11,900  99.0 0.88                                                                             0.90   4.1 0.1                                                                              0.49 98.5  0   No color                                                                      change                    Comparative                                                                          5,050   99.0 0.93                                                                             1.3    4.0 3.5                                                                              0.48 96.0  0   Color change              example 33                                          in one min.               Comparative                                                                          6,100   89.0 0.86                                                                             0.90   4.1 3.0                                                                              0.35 42.0  12  Color change              example 34                                          in 5 min.                 Comparative                                                                          3,300   99.0 0.94                                                                             1.4    4.0 12 0.48 95.0  0   Color change              example 35                                          in 1 min.                 Comparative                                                                          4,300   99.0 0.94                                                                             1.4    4.1 6.0                                                                              0.48 96.0  0   Color change              example 36                                          in 1 min.                 Comparative                                                                          4,800   99.2 0.94                                                                             1.4    4.2 4.0                                                                              0.48 96.2  0   Color change              example 37                                          in 1 min.                 Comparative                                                                          4,900   99.0 0.94                                                                             1.4    4.1 4.1                                                                              0.48 96.0  0   Color change              example 38                                          in 1 min.                 Comparative                                                                          5,100   99.0 0.94                                                                             1.4    4.2 3.8                                                                              0.48 95.8  0   Color change              example 39                                          in 1                      __________________________________________________________________________                                                        min.                  

What is claimed is:
 1. A process for producing α-olefin polymers which comprises:(a) reacting one mol of an organoaluminum compound (A₁) with 0.1 to 8 mols of an electron donor (B₁) in a solvent at a temperature of -20° to 200° C., to obtain a solid product (I); (b) reacting this solid product (I) with TiCl₄ in a ratio (Al/Ti) of the number of atoms of aluminum to that of Ti in TiCl₄ of 0.05 to 10, at a temperature of 0° to 200° C., and thereafter removing the resulting liquid portion and TiCl₄ freed by washing, to obtain a solid product (II); (c) reacting 100 g of this solid product (II) with 10 to 1,000 g of an electron donor (B₂) and 10 to 1,000 g of an electron acceptor at a temperature of 40° to 200° C., to obtain a solid product (III); (d) combining 1 g of said solid product (III) with 0.1 to 500 g of an organoaluminum compound (A₂) and subjecting said combination to polymerization treatment with 0.01 to 5,000 g of an α-olefin, (e) adding to said 1 g of solid product (III) and said 0.1 to 500 g of organoaluminum compound (A₂) (either prior to or subsequent to said polymerization treatment with 0.01 to 5,000 g of an α-olefin) 0.05 to 10 g of a reaction product (G) obtained by reacting(1) 1 mol of an organoaluminum compound (A₃) with (2) 0.01 to 5 mols of an electron donor (B₃) (3) such reaction being carried out at a temperature of -30° to 100° C., to thereby establish a preliminary activated cataly (f) polymerizing an α-olefin or α-olefins in the present this preliminarily activated catalyst.
 2. A process according to claim 1 wherein the reaction temperature in step (b) is 10 to 90° C.
 3. A process according to claim 1 or 2 wherein said polymerization is carried out by gas phase polymerization.
 4. A process according to claim 1 or 2 wherein said polymerization is carried out by slurry polymerization followed by gas phase polymerization.
 5. A process according to claim 1 or 2 wherein said polymerization is carried out bulk polymerization followed by gas phase polymerization.
 6. A process according to claim 1 or 2 said organoaluminum compounds (A₁), (A₂) and (A₃) may be the same or different and are expressed by the general formula:

    AlR.sub.n R'.sub.n' X.sub.3-(n+n')

wherein R and R' each represent an alkyl, aryl, alkaryl, cycloalkyl or alkoxy group; X represents fluorine, chlorine, bromine or iodine; and n and n' each represent an optional number of 0<n+n'≦3.
 7. A process according to claim 1 or 2 wherein said electron donors (B₁), (B₂) and (B₃) may be the same or different and each are one or more members selected from the group consisting of ethers, alcohols, esters, aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines, amides, urea, thiourea, isocyanates, azo compounds, phosphines, phosphites, phosphinites, thioethers and thioalcohols.
 8. A process according to claim 1 or 2 wherein (B₁) and (B₂) are each composed mainly of ethers, and electron donors other than ethers are employed together with ethers.
 9. A process according to claim 1 or 2 wherein said electron acceptor is one or more members selected from the group consisting of anhydrous AlCl₃, SiCl₄, SnCl₂, SnCl₄, TiCl₄, ZrCl₄, PCl₃, PCl₅, VCl₄ and SbCl₅.
 10. A process according to claim 1 or 2 wherein said solvent is an aliphatic hydrocarbon.
 11. A process according to claim 1 or 2 wherein said reaction of said reaction product (II) with said electron donor (B₂) and said electron acceptor is carried out in an aliphatic hydrocarbon.
 12. A process according to claim 1 or 2 wherein said reaction of said reaction product (II) with said electron donor (B₂) and said electron acceptor is carried out by reacting, in advance, said electron donor (B₂) with said electron acceptor at a temperature of 10° to 100° C. for 30 minutes to 2 hours, cooling the resulting reaction product down to 40° C. or lower and reacting this reaction product with said reaction product (II).
 13. A process according to claim 1 or 2 wherein said preparation of preliminarily activated catalyst according to steps (d) and (e) is carried out by combining said solid product (III) with said organoaluminum compound (A₂), subjecting the resulting combination to polymerization treatment with an α-olefin and thereafter adding said reaction product (G).
 14. A process according to claim 1 or 2 wherein said preparation of preliminarily activated catalyst according to steps (d) and (e) is carried out by combining said solid product (III) with said organoaluminum compound (A₂) in the presence of an α-olefin to thereby subject the former both to polymerization treatment with said α-olefin, and thereafter adding said reaction product (G).
 15. A process according to claim 13 wherein the material obtained by said polymerization treatment and consisting of said solid product (III), said organoaluminum compound (A₂) and a polymer of said α-olefin, and said solid product (G) are separately stored and mixed together just before the polymerization of step (f) and employed as the catalyst therefor.
 16. A process according to claim 1 or 2 wherein said preparation of preliminary activated catalyst according to steps (d) and (e) is carried out by combining said solid product (III) with said organoaluminum compound (A₂), adding the resulting combination to said solid product (G), and thereafter subjecting the mixture to polymerization treatment with 0.01-5,000 g of an α-olefin.
 17. A process according to claim 1 or 2 wherein said preparation of preliminarily activated catalyst according to steps (d) and (e) is carried out by combining said solid product (III) with said organoaluminum compound (A₂), adding the resulting combination to part of said reaction product (G), subjecting the resulting mixture to polymerization treatment with an 0.01-5,000 g of an α-olefin and thereafter further adding the remainder of said reaction product (G) to the thus treated material.
 18. A process according to claim 1 or 2 wherein said polymerization treatment is carried out so that the polymerized amount of said α-olefin in step (d) is 0.01 to 2,000 g per g of said solid product (III).
 19. A process for producing α-olefin polymers which comprises:(a) reacting one mol of an organoaluminum compound (A₁) with 1 to 4 mols of an electron donor (B₁) in 0.5 to 5 l of an aliphatic hydrocarbon solvent at a temperature of -10° to 100° C., to obtain a solid product (I); (b) reacting this solid product (I) with TiCl₄ in a ratio (Al/Ti) of the number of atoms of aluminum to that of Ti in TiCl₄ of 0.06 to 0.2, at a temperature of 10° to 90° C., and thereafter removing the resulting liquid portion and TiCl₄ freed by washing, to obtain a solid product (II); (c) reacting 100 g of this solid product (II) with 50 to 200 g of an electron donor (B₂) and 20 to 500 g of an electron acceptor in 0.1 to 1 l of an aliphatic hydrocarbon at a temperature of 50 ° to 100° C. to obtain a solid product (III); (d) combining 1 g of said solid product (III) and said 0.5 to 50 g of organoaluminum compound (A₂) (either prior to or subsequent to said polymerization treatment with 0.01 to 5,000 g of an α-olefin) with 0.05 to 10 g of a reaction product (G) obtained by reacting(1) 1 mol of an organoaluminum compound (A₃) with (2) 0.01 to 5 mols of an electron donor (B₃) (3) such reaction being carried out at a temperature of -30° to 100° C., to thereby establish a preliminary activated catalyst; and (f) polymerizing an α-olefin or α-olefins in the presence of this preliminarily activated catalyst.
 20. A process according to claim 14 wherein the material obtained by said polymerization treatment and consisting of said solid product (III), said organoaluminum compound (A₂) and a polymer of said α-olefin, and said solid product (G) are separately stored and mixed together just before the polymerization of step (f) and employed as the catalyst therefor. 